Substituted 1,3,5-triazinyl-(6)-aminophenyl-arsenic compounds



Patented Dec. 4, 1945 UNITED STATES PATENT OFFICE SUBSTITUTED 1,3,5-TRIAZINYL- (6) -AMINO- PHENYL-ARSENIC COMPOUNDS Ernst A. H. Friedheim, New York, N. Y.

No Drawing. Application June 3, 1944, Serial No. 538,695

9 Claims. (Cl. 260-242) n 'D J (IJF V M I with an aromatic rganic compound containing trivalent arsenic and corresponding to the formula WCsHz(A,B )--As--X.

In these formulas, W is an amino-group or halogen. If W is an aminoegroup, at least one of the groups D, E, F, is a halogen-group. If W is a halgen,,at least one of the groups D, E, F is an amino-group. In both cases the other groups are selected from the group consisting of halogen, NHz, NH Alk., N A1k.2, hydroxy-alkylamino, NCI-IzCHOHCHzOH, dialkyl-amino-alkylamino, and aminoacyl radicals, such as NHCOCHs and NHCOCsHs; the racials A and B are selected from the group consisting of hydrogen, halogen, OH, 0 Alk., O acyl, N02, NH2, NH A1k., N Alk.2, aminoacyl, and alkyl radicals; X is a divalent group selected from the group consisting of O, S, dihalides, such as C12, I2 or B112, and sulfur-containing radicals of the type =(SR)2 wherein R is an organic radical which is capable of carrying an SH-radical. Such sulfur-containing reactants are, for example, thioglycollic acid, cysteine, or glutathione, thiophenol. As examples of the trivalent arsenic compounds to be used according to my invention, the following may be mentioned: 4-amino-phenylarsinoxide,

4 chlor-phenylarsinoxide, 4 amino phenylarsindichloride, 4 amino-phenyl-arsinsulfide, amino-4-oxy-phenylarsinoxide. The condensation products thus formed have the formula N wherein Y and Y are each a radical selected from the group consisting of halogen, NHz, NH Alk., N A1k.2, hydroxy-alkyl-amino,

dialkyl-amino-alkyl-amino, and aminoacyl radicals; A and B are selected from the group consisting of hydrogen, halogen, OH, O Alk., O acyl, N02, NH2, NH Alk., N Alk.2, amino-acyl, and alkyl radicals, and X is a divalent radical selected from the group consisting of O, S, dihalides, sulfur-containing groups of the type =(SR)2; wherein R is an organic radical which is capa-' ble of carrying an SH-radical, and groups having the formula In carrying out the present invention, for example an aqueous solution containing one mol of 4-oxy-B-amino-phenyl-arsinoxide may be caused to react with a fine suspension of 1 mol of 2,4,6-trichloro-1,3,5-triazine in water at a temperature of 0 C. 'with the exclusion of oxygen. The resulting condensation product has the formula Subsequently, I this reaction product may be treated with a base selected from the group consisting of ammonia, alkyl amines, hydroxyl-alkyl amines and dialkyl-amino-alkyl amines. Similar reactions may be obtained by using a dihalide such as 4-amino-phenylarsindichloride instead of 4-oxy-3-amino-phenylarsinoxide. Instead of the latter, its derivatives or isomers, such as, for instance, 2-oxy-4-amino-phenyl-arsinoxide, or 4-amino-3-oxy-phenylarsinoxide may also be used. In carrying out these reactions, instead of the trichloro-triazine other derivatives of 1,3,5-triazine corresponding to the formula referred to above may also be used.

I have further found that the condensation products according to this invention may also be obtained by first forming a condensation product of the type disclosed in my above mentioned U. S. Patent No. 2,295,574 from a derivative of 1,3,5-triazine and a substituted phenyl-arsonic acid, and converting the condensation product thus obtained, into a compound containing trivalent arsenic. I have found that such conversion can be performed without the disintegration of the basic triazinyl-aminobenzene structure by treating the triazinyl-aminobenzenearsonic acid condensation product in hydrochloric acid solution, in the presence of hydriodic acid, with S02, hypophosphorous acid (H2PO3), or stannous chloride, or in neutral or alkaline solution with phenyl-hydrazine or sodium hydrosulfite (Na2S2O4). The reduction with $02 or phenylhydrazine leads to the arsinoxides, or dihalogenarsines, while the treatment with stannous chloride, hypophosphorous acid, and sodium hydrosulfite leads to the corresponding arsenocompounds.

For example, one part by weight of 2,4-diamino-1,3,5-triazinyl- (6) [amino-3-oxy-4-phenylarsonic acid I} is dissolved at about 80 C. in 100 parts of hydrochloric acid of sp. gr. 1.19. To the clear, warm solution /30 part of sodium iodide is added, and a stream of S02 gas is allowed to pass through the solution. After a few minutes the solution becomes cloudy, and the hydrochloride of 2,4 diamino 1,3,5-triazinyl- (6) -oxyamino phenylarsindichloride separates out in crystalline form. It is soluble in ethyl alcohol from which it may be recrystallized. It is slight- 1y soluble in acetone, and insoluble in chloroform, CCh and benzene. The corresponding arsinoxide is formed by the action of alkali, such as dilute ammonia or sodium bicarbonate on the arsindichloride.

An arseno-compound can be obtained by the action of stannous chloride on 2,4-diamino-triazinyl-(G) -[4-oxy-3 amino-phenylarsonic acid I]. One part of the latter is suspended in 50 parts of aqueous hydrochloric acid of 1.19 density containing about 50% stannous chloride, and 1% of hydriodic acid. On gentle warming the substance goes slowly into solution, the reaction mixture taking a yellow color. It becomes cloudy, and on standing a yellow precipitate separates, which represents the hydrochloride of the bis- ,'-4,4'-tetraamino-triazinyl- (6-6') ]-3-3' diamino-4-4'-dioxyarseno-benzene of the formula This compound is moderately soluble in dilute hydrochloric acid, and insoluble in ether and chloroform.

Other compounds according to my present invention may be obtained by applying the above described reduction processes to other arsonoanilino-triazine compounds, such as monochlormonoamino-arsono-anilino-triazine, and other arsono-anilino-triazine compounds obtained according to my above mentioned U. S. Patent No. 2,295,574.

As described in Example 2 of my above men tioned U. S. Patent No. 2,295,574, p- [2,4-dich1oro- 1,3,5 triazi'nyl (6)] aminophenylarsonic acid may be treated with ammonia in order to convert itinto a 2-chloro-4-amino-compound by covering said dichloro-compound with 10 times the quantity of 10% aqueous ammonia, and shaking at 45 C. for 1 hour, whereby the product goes into complete solution. By heating the [2- chloro-4-amino-1,3,5-triaziny1- (6) l-amino-phenyl-arsonic compound in hydrochloric acid solution with S02, 2. compound of the formula.

I (ll-C 10 parts by weight of this precipitate are dissolved at -80 C. in 1000 parts by weight of hydrochloric acid of sp. gr. 1.19, and the solution is subjected to the action of stannous chlo- Similar products but containing in the triazine ring halogen substituents and/or amino or substituted amino radicals linked to the carbon atoms of the triazine ring, may be obtained by reacting the above mentioned 6-nitro-4-amino- 3-methoxy-phenyl-arsonic acid with one halogen atom of cyanuric chloride, and subjecting the condensation product thus formed to reduction. 01' one or both halogen atoms of the condensation product may be first reacted with a base selected from the group consisting of ammonia, alkyl amines, hydroxy-alkyl amines and dialkylamino-alkyl-amines and the resulting reaction product may then be subjected to reduction in the above described manner,

Furthermore, other similar compounds embodying the present invention may be obtained, for example, by subjecting cyanuric chloride or 2,4-diamino-6-chloro-1,3,5-triazine to condensation in the above described manner with aminophenyl-arsonic acid compounds substituted in the benzene ring by a nitro-group or by a nitrogroup and a halogen, hydroxy-O-acyl, or alkyl roup and subjecting said nitro-group and the arsonic acid group of the condensation product to reduction substantially in accordance with the above described procedure.

A compound of the formula may be, for example, prepared by condensing 3-nitro-4-amino-phenylarsonic acid with 2-,4-diamino-G-chloro-1,3,5-triazine, and subjecting the wherein one of Y and Y is an amino radical, while the other is selected from the group consisting of halogen radicals and amino radicals; Cs represents a benzene ring, one of A and B is an amino radical, while the other is selected from the group consisting of hydrogen, halogen, OH, O-alkyl, O-acyl, and alkyl radicals; X is a divalent radical selected from the group consisting of O, S and dihalides.

2. A 1,3,5-triazine derivative of the formula wherein Ca represents a benzene ring, one of A and B is an amino radical, While the other is selected from th group consisting of hydrogen, halogen, OH, O-alkyl, O-acyl, and alkyl radicals; X is a divalent radical selected from the group consisting of O, S and dihalides.

- 3. A 1,-3,5-tri azine derivative of theformula I c if \N NH,- 'J N -Nn-o.m(mmfiis x wherein C6 represents a benzene ring, one of A and B is an amino radical, while the other is selected from the group consisting of hydrogen, halogen, OH, O-alkyl, O-acyl, and alkyl radicals; X is a divalent radical selected from the group consisting of O, S and dihalides.

4. A 1,3,5-triazine derivative of the formula nu,

l 5 NH5C\ /C-NHCsHz(A,B )-ASC12 N p wherein Cs represents a benzene ring, and one of A and B is an amino radical, while the other is selected from the group consisting of hydrogen, halogen, OH, O-alkyl, -O-acyl, and alkyl radicals.

5. A 1,3,5-triazine derivative of the formula I /G\ N/ N wherein C6 represents a benzene ring, and one of A and B is an amino radical, while the other is selected from the group consisting of hydrogen, halogen, OH, O-alkyl, O-acyl, and alkyl radicals.

, 6. A process for the preparation of a 1,3,5- triazine derivative as claimed in claim 1, said process comprising subjecting in aqueous solution a 1,3,5-triazine derivative of the formula 7. A process for the preparation of a 1,3,5-

triazine compound of the formula wherein one of Y and Y is an amino radical,

while the other is selected from the group consisting of halogen radicals and amino radicals;

Cs represents a benzene ring; one of A and B is an amino radical, while the other is selected from the group consisting of hydrogen, halogen, --OH, O-alkyl, O-acyl and alkyl radicals, said process comprising mibject sin aqueous omtion a. 1,3,5-triazine derivative of the formula to the action of SO: in the presence of hydrochloric acid and hydriodic acid,

8. A process for the preparation of a 1,3,5- triazine compound of the formula wherein one of Y and Y is an amino radical, while the other is selected from the group consisting of halogen radicals and amio radicals; Cs represents a benzene ring; one of A and B is an amino radical, while the other is selected from the group consisting of hydrogen, halogen, --OH, O-alky1, -O-acy1 and alkyl radicals, said process comprising subjecting in aqueous solution a 1,3,5-triazine derivative of the formula to the action of stannous chloride in aqueous hydrochloric acid solution. 9.-A process for .the preparation of a 1 .3,5-. triazine compound of ,the formula I I N/ N W;

to the action of a reducing agent in aqueous hydrochloric acid solution.

ERNST A. H. FRIEDHEm. 

